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US20080006377A1 - Stabilised Aluminosilicate Slurries - Google Patents

Stabilised Aluminosilicate Slurries Download PDF

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Publication number
US20080006377A1
US20080006377A1 US11/568,903 US56890305A US2008006377A1 US 20080006377 A1 US20080006377 A1 US 20080006377A1 US 56890305 A US56890305 A US 56890305A US 2008006377 A1 US2008006377 A1 US 2008006377A1
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Prior art keywords
silica
aqueous slurry
crystalline aluminosilicate
slurry according
range
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US11/568,903
Inventor
Simon Stebbing
Stephen Ellison
Alexis Toft
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PQ Silicas UK Ltd
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Ineos Silicas Ltd
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Assigned to INEOS SILICAS LIMITED reassignment INEOS SILICAS LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ELLISON, STEPHEN GEORGE, STEBBING, SIMON RICHARD, TOFT, ALEXIS JOHN
Publication of US20080006377A1 publication Critical patent/US20080006377A1/en
Assigned to PQ SILICAS UK LIMITED reassignment PQ SILICAS UK LIMITED ASSIGNMENT OF U.S. PATENTS Assignors: INEOS SILICAS LIMITED
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/14—Type A
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/22—Type X
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Definitions

  • This invention relates to aqueous slurries of crystalline aluminosilicates and in particular to crystalline aluminosilicate slurries having controlled rheological properties.
  • Crystalline aluminosilicates, or zeolites have found use as fillers in such applications as the manufacture of paper. For such use, it is convenient to transport the zeolite in bulk in the form of an aqueous slurry.
  • Particularly useful aqueous zeolite slurries having a relatively low pH value and containing a multivalent salt in addition to the zeolite are described in PCT application published as WO 01/94512. These slurries are stable and do not settle on standing but, because they have a lightly gelled structure, they can sometimes be difficult to fully discharge fully from a vessel.
  • An object of this invention is to provide a modified version of such a slurry having a structure which is resistant to settling but is readily capable of being discharged from a vessel.
  • an aqueous slurry comprises
  • M represents a first metal moiety, said first metal having a valency of n, x is the molar ratio of silica to alumina and y indicates the molar ratio of water to alumina,
  • the silica has a BET surface area greater than 500 m 2 /g and a pore volume, as measured by nitrogen manometry of less than 2.1 cm 3 /g.
  • the first metal M can be any metal capable of forming a crystalline aluminosilicate structure having the above empirical formula.
  • M is an alkali metal and the preferred alkali metal is sodium.
  • the crystalline aluminosilicates used in the invention are usually known as zeolites and can have the structure of any of the known zeolites.
  • the structure and characteristics of many zeolites are described in the standard work “Zeolite Molecular Sieves” by Donald W. Breck, published by Robert E. Krieger Publishing Company.
  • x in the above empirical formula is in the range 1.5 to 10.
  • Zeolites useful in this invention may be based on naturally-occurring or synthetic aluminosilicates and the preferred forms of zeolite have the structure known as zeolite P, zeolite X or zeolite A.
  • Particularly preferred forms of zeolite are those disclosed in EP-A-0 384 070, EP-A-0 565 364, EP-A-0 697 010, EP-A-0 742 780, WO-A-96/14270, WO-A-96/34828 and WO-A-97/06102, the entire contents of which are incorporated herein by this reference.
  • the zeolite P described in EP-A-0 384 070 has the empirical formula given above in which M represents an alkali metal and x has a value up to 2.66, preferably in the range 1.8 to 2.66, and has a structure which is particularly useful in the present invention.
  • Slurries useful in the paper industry preferably have an approximately neutral pH.
  • Particularly useful slurries of this invention contain an amount of the mineral or organic acid which is sufficient to produce a slurry having a pH in the range 6 to 9, preferably in the range 7 to 9.
  • the particle size of the crystalline aluminosilicates used in the slurries of this invention is adjusted to suit the intended use.
  • the volume average particle size will be greater than 0.1 ⁇ m and, usually, less than 20 ⁇ m. More preferably, the crystalline aluminosilicates will have a volume average particle size in the range 0.5 to 10 ⁇ m.
  • the crystalline aluminosilicate preferably has a volume average particle size in the range 1 to 5 ⁇ m.
  • a size distribution is obtained by light scattering from particles dispersed by ultrasound in demineralised water using a Malvern Mastersizer®.
  • the volume average particle size is the average particle size at 50 percent cumulative volume as determined from the distribution.
  • the amount of crystalline aluminosilicate, expressed as dry weight of aluminosilicate present in the slurry is usually above 20 percent by weight and often above 30 percent by weight.
  • the upper practical limit on the amount of aluminosilicate in the slurry will depend upon the viscosity of the slurry, which is likely to be too high for use in many applications when more than 65 percent dry weight of aluminosilicate is present.
  • the amount of crystalline aluminosilicate, expressed as dry weight of aluminosilicate present in the slurry is in the range 43 to 60 percent by weight, more preferably 43 to 55 percent by weight, most preferably 43 to 52 percent by weight.
  • dry aluminosilicate is considered to be aluminosilicate which has been heated at 105° C. to constant weight.
  • Suitable mineral acids include sulphuric acid, hydrochloric acid and nitric acid.
  • An example of a suitable organic acid is acetic acid.
  • the slurry can also contain silica having a BET surface area greater than 500 m 2 /g.
  • the silica has a BET surface area greater than 550 m 2 /g, more preferably greater than 600 m 2 /g.
  • the surface area is less than 1200 m 2 /g.
  • the silica can also have a pore volume as measured by nitrogen manometry of less than 2.1 cm 3 /g.
  • the pore volume is less than 1.2 cm 3 /g, more preferably the pore volume is less than 0.5 cm 3 /g.
  • the silica is silica gel or a precipitated silica.
  • the silica preferably has a volume average particle size in the range 0.5 to 30 ⁇ m, as measured by Malvern Mastersizer®. More preferably, the volume average particle size of the silica is in the range 2 to 15 ⁇ m.
  • the silica is preferably present in the slurry in an amount in the range 0.2 to 40 percent by weight with respect to the dry weight of crystalline aluminosilicate. More preferably, the amount of silica present is in the range 0.5 to 15 percent by weight with respect to dry weight of crystalline aluminosilicate and frequently, the amount of silica used is in the range 0.2 to 5.0 percent by weight with respect to dry weight of crystalline aluminosilicate.
  • the crystalline aluminosilicate used in the invention can be prepared by a conventional process.
  • a zeolite of type A can be prepared by mixing together sodium aluminate and sodium silicate at a temperature within the range of ambient temperature up to boiling point to form a gel, ageing the gel with stirring at a temperature usually in the range 70 to 95° C., separating the crystalline sodium aluminosilicate thus formed, washing, generally at a pH in the range 10 to 12.5, and drying.
  • Zeolite of type P can be prepared by a similar process but zeolite type P formation is induced by the addition of type P seeds to the mixture of sodium aluminate and sodium silicate.
  • M represents a first metal moiety, said first metal having a valency of n, x is the molar ratio of silica to alumina and y indicates the molar ratio of water to alumina,
  • the slurry of the invention can be prepared in a number of ways.
  • the crystalline aluminosilicate, mineral or organic acid and water can be mixed in any order. Therefore, according to yet another aspect of the invention there is provided a method of making an aqueous slurry comprising mixing
  • M represents a first metal moiety, said first metal having a valency of n, x is the molar ratio of silica to alumina and y indicates the molar ratio of water to alumina,
  • a preferred method comprises forming a precursor slurry containing the acid and the crystalline aluminosilicate and subsequently adding the silica.
  • the volume average particle size of the silica is determined using a Malvern Mastersizer® model S, with a 300 RF lens and MS17 sample presentation unit.
  • This instrument made by Malvern Instruments, Malvern, Worcestershire uses the principle of Fraunhofer diffraction, utilising a low power He/Ne laser. Before measurement the sample is dispersed ultrasonically at 25 W ultrasound power in demineralised water for 5 minutes to form an aqueous suspension.
  • the Malvern Mastersizer® measures the volume particle size distribution of the silica.
  • the volume average particle size (d 50 ) or 50 percentile is easily obtained from the data generated by the instrument. Other percentiles, such as the 90 percentile (d 90 ), are readily obtained.
  • Zeolite A24 is a P type zeolite sold by INEOS Silicas Limited under the trade mark Doucil A24. It had a volume average particle size as measured by Malvern Mastersizer® of 1.5 ⁇ m.
  • the silica was a silica gel sold by INEOS Silicas Limited under the Trade Name Sorbosil AC30. It had a volume average particle size of 7.9 ⁇ m, a pore volume to nitrogen of 0.39 cm 3 g ⁇ 1 and BET surface area of 725 m 2 g ⁇ 1 .
  • Sulphuric acid was received at 40 weight percent and diluted with demineralised water to 10 weight percent before being added to the mixtures.
  • the amount of acid added is expressed at 100 weight percent in Table 1.
  • the rheological properties of the slurries were determined immediately after the slurries were prepared using a Mettler Toledo RM 180 Rheomat rheometer, at 22 ⁇ 1° C., with a Mooney cup and bob geometry. The samples were shaken by hand prior to measurement but were not sheared vigorously. The rheometer programme consisted of shearing the sample at a set shear rate for 30 seconds, after which a shear stress measurement was taken at that shear rate. Measurements were taken at 10, 20, 30, 40, 60, 100, 200, 350 and 500 s ⁇ 1 . The Brookfield viscosity measurements were also carried out at 22 ⁇ 1° C., with the viscosity being recorded after 1 minute of shearing at 20 rpm. The spindle chosen for each sample is indicated in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Paper (AREA)

Abstract

An aqueous slurry comprises (a) a crystalline aluminosilicate represented by the empirical formula M2/nO.Al2O3.xSiO2.yH2O wherein M represents a first metal moiety, said first metal having a valency of n, x is the molar ratio of silica to alumina and y indicates the molar ratio of water to alumina, (b) a mineral or organic acid, and (c) particulate silica. The silica may have a BET surface area greater than 500 m2/g and a pore volume, as measured by nitrogen manometry of less than 2.1 cm3/g. The slurry is stable on storage but has a low viscosity at low shear rate.

Description

  • This invention relates to aqueous slurries of crystalline aluminosilicates and in particular to crystalline aluminosilicate slurries having controlled rheological properties.
  • Crystalline aluminosilicates, or zeolites, have found use as fillers in such applications as the manufacture of paper. For such use, it is convenient to transport the zeolite in bulk in the form of an aqueous slurry. Particularly useful aqueous zeolite slurries having a relatively low pH value and containing a multivalent salt in addition to the zeolite are described in PCT application published as WO 01/94512. These slurries are stable and do not settle on standing but, because they have a lightly gelled structure, they can sometimes be difficult to fully discharge fully from a vessel.
  • An object of this invention is to provide a modified version of such a slurry having a structure which is resistant to settling but is readily capable of being discharged from a vessel.
  • According to the invention, an aqueous slurry comprises
      • (a) a crystalline aluminosilicate represented by the empirical formula
        M2/nO.Al2O3.xSiO2.yH2O
  • wherein M represents a first metal moiety, said first metal having a valency of n, x is the molar ratio of silica to alumina and y indicates the molar ratio of water to alumina,
      • (b) a mineral or organic acid, and
      • (c) particulate silica.
  • Generally, the silica has a BET surface area greater than 500 m2/g and a pore volume, as measured by nitrogen manometry of less than 2.1 cm3/g.
  • The above form of empirical formula is used for simplicity in expressing the molar ratios of the components, but it can be seen that the ratio of Si atoms to Al atoms in this formula is equal to x/2 and the ratio of water molecules to Al atoms is equal to y/2.
  • The first metal M can be any metal capable of forming a crystalline aluminosilicate structure having the above empirical formula. Preferably, M is an alkali metal and the preferred alkali metal is sodium.
  • The crystalline aluminosilicates used in the invention are usually known as zeolites and can have the structure of any of the known zeolites. The structure and characteristics of many zeolites are described in the standard work “Zeolite Molecular Sieves” by Donald W. Breck, published by Robert E. Krieger Publishing Company. Usually, the value of x in the above empirical formula is in the range 1.5 to 10. The value of y, which represents the amount of water contained in the voids of the zeolite, can vary widely. In anhydrous material y=0 and, in fully hydrated zeolites, y is typically up to 5.
  • Zeolites useful in this invention may be based on naturally-occurring or synthetic aluminosilicates and the preferred forms of zeolite have the structure known as zeolite P, zeolite X or zeolite A. Particularly preferred forms of zeolite are those disclosed in EP-A-0 384 070, EP-A-0 565 364, EP-A-0 697 010, EP-A-0 742 780, WO-A-96/14270, WO-A-96/34828 and WO-A-97/06102, the entire contents of which are incorporated herein by this reference. The zeolite P described in EP-A-0 384 070 has the empirical formula given above in which M represents an alkali metal and x has a value up to 2.66, preferably in the range 1.8 to 2.66, and has a structure which is particularly useful in the present invention.
  • Slurries useful in the paper industry preferably have an approximately neutral pH. Particularly useful slurries of this invention contain an amount of the mineral or organic acid which is sufficient to produce a slurry having a pH in the range 6 to 9, preferably in the range 7 to 9.
  • The particle size of the crystalline aluminosilicates used in the slurries of this invention is adjusted to suit the intended use. Typically, the volume average particle size will be greater than 0.1 μm and, usually, less than 20 μm. More preferably, the crystalline aluminosilicates will have a volume average particle size in the range 0.5 to 10 μm. For use as a filler for papers, the crystalline aluminosilicate preferably has a volume average particle size in the range 1 to 5 μm.
  • Various methods of assessing particle size are known and all give slightly different results. In the present invention, a size distribution is obtained by light scattering from particles dispersed by ultrasound in demineralised water using a Malvern Mastersizer®. The volume average particle size is the average particle size at 50 percent cumulative volume as determined from the distribution.
  • The amount of crystalline aluminosilicate, expressed as dry weight of aluminosilicate present in the slurry is usually above 20 percent by weight and often above 30 percent by weight. The upper practical limit on the amount of aluminosilicate in the slurry will depend upon the viscosity of the slurry, which is likely to be too high for use in many applications when more than 65 percent dry weight of aluminosilicate is present. Preferably, the amount of crystalline aluminosilicate, expressed as dry weight of aluminosilicate present in the slurry, is in the range 43 to 60 percent by weight, more preferably 43 to 55 percent by weight, most preferably 43 to 52 percent by weight. For the purposes of this invention dry aluminosilicate is considered to be aluminosilicate which has been heated at 105° C. to constant weight.
  • Examples of suitable mineral acids include sulphuric acid, hydrochloric acid and nitric acid. An example of a suitable organic acid is acetic acid.
  • The slurry can also contain silica having a BET surface area greater than 500 m2/g. Preferably the silica has a BET surface area greater than 550 m2/g, more preferably greater than 600 m2/g. Usually the surface area is less than 1200 m2/g.
  • The silica can also have a pore volume as measured by nitrogen manometry of less than 2.1 cm3/g. Preferably, the pore volume is less than 1.2 cm3/g, more preferably the pore volume is less than 0.5 cm3/g.
  • Preferably, the silica is silica gel or a precipitated silica.
  • The silica preferably has a volume average particle size in the range 0.5 to 30 μm, as measured by Malvern Mastersizer®. More preferably, the volume average particle size of the silica is in the range 2 to 15 μm.
  • The silica is preferably present in the slurry in an amount in the range 0.2 to 40 percent by weight with respect to the dry weight of crystalline aluminosilicate. More preferably, the amount of silica present is in the range 0.5 to 15 percent by weight with respect to dry weight of crystalline aluminosilicate and frequently, the amount of silica used is in the range 0.2 to 5.0 percent by weight with respect to dry weight of crystalline aluminosilicate.
  • The crystalline aluminosilicate used in the invention can be prepared by a conventional process. For example, a zeolite of type A can be prepared by mixing together sodium aluminate and sodium silicate at a temperature within the range of ambient temperature up to boiling point to form a gel, ageing the gel with stirring at a temperature usually in the range 70 to 95° C., separating the crystalline sodium aluminosilicate thus formed, washing, generally at a pH in the range 10 to 12.5, and drying. Zeolite of type P can be prepared by a similar process but zeolite type P formation is induced by the addition of type P seeds to the mixture of sodium aluminate and sodium silicate.
  • According to another aspect of the invention there is provided the use, in the manufacture of paper, of an aqueous slurry comprising
      • (a) a crystalline aluminosilicate represented by the empirical formula
        M2/nO.Al2O3.xSiO2.yH2O
  • wherein M represents a first metal moiety, said first metal having a valency of n, x is the molar ratio of silica to alumina and y indicates the molar ratio of water to alumina,
      • (b) a mineral or organic acid, and
      • (c) particulate silica.
  • The slurry of the invention can be prepared in a number of ways. The crystalline aluminosilicate, mineral or organic acid and water can be mixed in any order. Therefore, according to yet another aspect of the invention there is provided a method of making an aqueous slurry comprising mixing
      • (a) a crystalline aluminosilicate represented by the empirical formula
        M2/nO.Al2O3.xSiO2.yH2O
  • wherein M represents a first metal moiety, said first metal having a valency of n, x is the molar ratio of silica to alumina and y indicates the molar ratio of water to alumina,
      • (b) a mineral or organic acid,
      • (c) particulate silica, and
      • (d) water
  • together to produce a slurry. A preferred method, however, comprises forming a precursor slurry containing the acid and the crystalline aluminosilicate and subsequently adding the silica.
  • The following tests have been used in this invention.
  • BET Surface Area and Pore Volume
  • Surface area of the silicas were measured using standard nitrogen adsorption methods of Brunauer, Emmett and Teller (BET) using a multi-point method with an ASAP 2400 apparatus supplied by Micromeritics of USA. The method is consistent with the paper by S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc., 60, 309 (1938). The pore volume was determined by a single point method as described in the operation manual for the ASAP 2400 apparatus. Samples are outgassed under vacuum at 270° C. for 1 hour before measurement at about −196° C.
  • Volume Average Particle Size
  • The volume average particle size of the silica is determined using a Malvern Mastersizer® model S, with a 300 RF lens and MS17 sample presentation unit. This instrument, made by Malvern Instruments, Malvern, Worcestershire uses the principle of Fraunhofer diffraction, utilising a low power He/Ne laser. Before measurement the sample is dispersed ultrasonically at 25 W ultrasound power in demineralised water for 5 minutes to form an aqueous suspension. The Malvern Mastersizer® measures the volume particle size distribution of the silica. The volume average particle size (d50) or 50 percentile is easily obtained from the data generated by the instrument. Other percentiles, such as the 90 percentile (d90), are readily obtained.
  • The invention is illustrated by the following non-limiting examples.
    • EXAMPLE
  • Three slurries were prepared with the compositions given in Table 1 below.
    TABLE 1
    Sample
    A B C
    Demineralised Water/wt. % 47.8 49.3 48.6
    Al2(SO4)3•14 H2O/wt % 1.5 0 0
    Zeolite A24 (water content 7.03% 50 50 50
    by drying at 105° C.)/wt. %
    Silica/wt. % 0.7 0 0.7
    Sulphuric acid (100%)/wt. % 0 0.7 0.7
    Sample size/g 1000 200 250
    pH 7.64 8.12 8.05
    Dry solids (loss at 105)/wt. % 46.6 48.6
    Brookfield viscosity at 20 rpm/cps 3850 3700 955
    (spindle 4) (spindle 5) (spindle 3)
    Mettler viscosity at 20 sec − 1/Pa s 0.819 0.609 0.284
  • The amounts given above are parts by weight.
  • Zeolite A24 is a P type zeolite sold by INEOS Silicas Limited under the trade mark Doucil A24. It had a volume average particle size as measured by Malvern Mastersizer® of 1.5 μm.
  • The silica was a silica gel sold by INEOS Silicas Limited under the Trade Name Sorbosil AC30. It had a volume average particle size of 7.9 μm, a pore volume to nitrogen of 0.39 cm3g−1 and BET surface area of 725 m2g−1.
  • Sulphuric acid was received at 40 weight percent and diluted with demineralised water to 10 weight percent before being added to the mixtures. The amount of acid added is expressed at 100 weight percent in Table 1.
  • The rheological properties of the slurries were determined immediately after the slurries were prepared using a Mettler Toledo RM 180 Rheomat rheometer, at 22±1° C., with a Mooney cup and bob geometry. The samples were shaken by hand prior to measurement but were not sheared vigorously. The rheometer programme consisted of shearing the sample at a set shear rate for 30 seconds, after which a shear stress measurement was taken at that shear rate. Measurements were taken at 10, 20, 30, 40, 60, 100, 200, 350 and 500 s−1. The Brookfield viscosity measurements were also carried out at 22±1° C., with the viscosity being recorded after 1 minute of shearing at 20 rpm. The spindle chosen for each sample is indicated in Table 1.

Claims (19)

1. An aqueous slurry comprising:
(a) a crystalline aluminosilicate represented by the empirical formula

M2/nO.Al2O3.xSiO2.yH2O
wherein M represents a first metal moiety, said first metal having a valency of n, x is the molar ratio of silica to alumina, and y indicates the molar ratio of water to alumina;
(b) one of (i) a mineral acid and (ii) an organic acid; and
(c) particulate silica with a BET surface area greater than 500 m2/g and a pore volume, as measured by nitrogen manometry of less than 2.1 cm3/g.
2. An aqueous slurry according to claim 1 characterised in that M is sodium.
3. An aqueous slurry according to claim 1 characterised in that the crystalline aluminosilicate is one of a zeolite P, zeolite A, and zeolite X.
4. An aqueous slurry according to claim 1 in which the acid is sulphuric acid.
5. An aqueous slurry according to claim 1 characterised in that it has a pH in the range 6 to 9.
6. An aqueous slurry according to claim 1 characterised in that the crystalline aluminosilicate has a volume average particle size in the range 0.1 to 20 μm.
7. An aqueous slurry according to claim 1 characterised in that the amount of crystalline aluminosilicate present in the slurry is in the range 43 to 60 percent by weight calculated as dry aluminosilicate.
8. An aqueous slurry according claim 1 in which the silica has a BET surface area greater than 550 m2/g.
9. An aqueous slurry according to claim 1 characterised in that the silica has a pore volume of less than 1.2 cm3/g.
10. An aqueous slurry according to claim 1 characterised in that the silica has a volume average particle size in the range 0.5 to 30 μm.
11. An aqueous slurry according to any claim 1 characterised in that the amount of silica present in the slurry is in the range 0.2 to 40 percent by weight with respect to dry weight of crystalline aluminosilicate present.
12-14. (canceled)
15. An aqueous slurry according to claim 7 characterised in that the amount of crystalline aluminosilicate present in the slurry is in the range 43 to 55 percent by weight calculated as dry aluminosilicate.
16. An aqueous slurry according to claim 15 characterised in that the amount of crystalline aluminosilicate present in the slurry is in the range 43 to 52 percent by weight calculated as dry aluminosilicate.
17. An aqueous slurry according claim 8 in which the silica has a BET surface area greater than 600 m2/g.
18. An aqueous slurry according claim 9 characterised in that the silica has a pore volume of less than 0.5 cm3/g.
19. A method for manufacturing paper comprising using an aqueous slurry that comprises:
(a) a crystalline aluminosilicate represented by the empirical formula

M2/nO.Al2O3.xSiO2.yH2O
wherein M represents a first metal moiety, said first metal having a valency of n, x is the molar ratio of silica to alumina, and y indicates the molar ratio of water to alumina;
(b) one of (i) a mineral acid and (ii) an organic acid; and
(c) particulate silica with a BET surface area greater than 500 m2/g and a pore volume, as measured by nitrogen manometry of less than 2.1 cm3/g.
20. A method of making an aqueous slurry comprising mixing
(a) a crystalline aluminosilicate represented by the empirical formula

M2/nO.Al2O3.xSiO2.yH2O
wherein M represents a first metal moiety, said first metal having a valency of n, x is the molar ratio of silica to alumina, and y indicates the molar ratio of water to alumina,
(b) one of (i) a mineral acid and (ii) an organic acid,
(c) particulate silica with a BET surface area greater than 500 m2/g and a pore volume, as measured by nitrogen manometry of less than 2.1 cm3/g, and
(d) water together to produce a slurry.
21. A method according to claim 20 in which the water, aluminosilicate and acid are mixed to form a precursor slurry, and the silica is added to the precursor slurry.
US11/568,903 2004-05-13 2005-05-06 Stabilised Aluminosilicate Slurries Abandoned US20080006377A1 (en)

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GBGB0410697.7A GB0410697D0 (en) 2004-05-13 2004-05-13 Stabilised aluminosilicate slurries
GB0410697.7 2004-05-13
PCT/GB2005/001728 WO2005110920A1 (en) 2004-05-13 2005-05-06 Stabilised aluminosilicate slurries

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Publication number Priority date Publication date Assignee Title
US10815358B2 (en) 2016-09-09 2020-10-27 Lg Chem, Ltd. Reinforcing material for rubber comprising aluminosilicate particles and rubber composition for tires comprising the same
US10875980B2 (en) 2016-09-09 2020-12-29 Lg Chem, Ltd. Reinforcing material for rubber comprising aluminosilicate particles and rubber composition for tires comprising the same

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US4405484A (en) * 1980-08-12 1983-09-20 Toyo Soda Manufacturing Co., Ltd. Zeolite powder having high flowability, process for preparing same and detergent composition containing same
US4405483A (en) * 1982-04-27 1983-09-20 The Procter & Gamble Company Stable liquid detergents containing aluminosilicate ion exchange material
US4622166A (en) * 1982-03-17 1986-11-11 Mizusawa Kagaku Kogyo Kabushiki Kaisha Process for preparation of zeolite slurry excellent in static stability and dynamic stability
US5206195A (en) * 1990-05-31 1993-04-27 Kanebo Ltd. Stablized synthetic zeolite and a process for the preparation thereof
US6670311B1 (en) * 1998-08-28 2003-12-30 Quest International Bv Granular compositions

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US4405484A (en) * 1980-08-12 1983-09-20 Toyo Soda Manufacturing Co., Ltd. Zeolite powder having high flowability, process for preparing same and detergent composition containing same
US4622166A (en) * 1982-03-17 1986-11-11 Mizusawa Kagaku Kogyo Kabushiki Kaisha Process for preparation of zeolite slurry excellent in static stability and dynamic stability
US4405483A (en) * 1982-04-27 1983-09-20 The Procter & Gamble Company Stable liquid detergents containing aluminosilicate ion exchange material
US5206195A (en) * 1990-05-31 1993-04-27 Kanebo Ltd. Stablized synthetic zeolite and a process for the preparation thereof
US6670311B1 (en) * 1998-08-28 2003-12-30 Quest International Bv Granular compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10815358B2 (en) 2016-09-09 2020-10-27 Lg Chem, Ltd. Reinforcing material for rubber comprising aluminosilicate particles and rubber composition for tires comprising the same
US10875980B2 (en) 2016-09-09 2020-12-29 Lg Chem, Ltd. Reinforcing material for rubber comprising aluminosilicate particles and rubber composition for tires comprising the same

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CN1997592A (en) 2007-07-11
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AU2005243854A1 (en) 2005-11-24
EP1744989A1 (en) 2007-01-24
CA2565696A1 (en) 2005-11-24
BRPI0511042A (en) 2007-11-27
DE602005013762D1 (en) 2009-05-20
EP1744989B1 (en) 2009-04-08
GB0410697D0 (en) 2004-06-16
ZA200609334B (en) 2008-06-25
CN1997592B (en) 2011-03-30
MY142271A (en) 2010-11-15
ATE427912T1 (en) 2009-04-15
PL1744989T3 (en) 2009-10-30
ES2324881T3 (en) 2009-08-18
WO2005110920A1 (en) 2005-11-24
KR20070014197A (en) 2007-01-31

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